Thin film transistors (TFTs) are widely used as switching elements in electronics, for example, in active-matrix liquid-crystal displays, smart cards, and a variety of other electronic devices and components thereof. The thin film transistor (TFT) is an example of a field effect transistor (FET). The best-known example of an FET is the MOSFET (Metal-Oxide-Semiconductor-FET), today's conventional switching element for high-speed applications. Presently, most thin film devices are made using amorphous silicon as the semiconductor. Amorphous silicon is a less expensive alternative to crystalline silicon. This fact is especially important for reducing the cost of transistors in large-area applications. Application of amorphous silicon is limited to relatively low speed devices, however, since its maximum mobility (0.5-1.0 cm2/V sec) is about a thousand times smaller than that of crystalline silicon.
Although amorphous silicon is less expensive than highly crystalline silicon for use in TFTs, amorphous silicon still has its drawbacks. The deposition of amorphous silicon, during the manufacture of transistors, requires relatively costly processes, such as plasma enhanced chemical vapor deposition and high temperatures (about 360° C.) to achieve the electrical characteristics sufficient for display applications. Such high processing temperatures disallow the use of substrates, for deposition, made of certain plastics that might otherwise be desirable for use in applications such as flexible displays.
In the past decade, organic materials have received attention as a potential alternative to inorganic materials such as amorphous silicon for use in semiconductor channels of TFTs. Organic semiconductor materials are simpler to process, especially those that are soluble in organic solvents and, therefore, capable of being applied to large areas by far less expensive processes, such as spin coating, dip coating and microcontact printing. Furthermore organic materials may be deposited at lower temperatures, opening up a wider range of substrate materials, including plastics, for flexible electronic devices. Accordingly, thin film transistors made of organic materials can be viewed as a potential key technology for plastic circuitry in display drivers, portable computers, pagers, memory elements in transaction cards, and identification tags, and the like, where ease of fabrication, mechanical flexibility, and/or moderate operating temperatures are important considerations.
Considerable efforts have been made to discover new organic semiconductor materials that can be used in TFTs to provide the switching and/or logic elements in electronic components, many of which require significant mobilities, well above 0.01 cm2/Vs, and current on/off ratios (hereinafter referred to as “on/off ratios”) greater than 1000. Organic TFTs having such properties are capable of use for electronic applications such as pixel drivers for displays and identification tags. Most of the compounds exhibiting these desirable properties are “p-type” or “p-channel,” however, meaning that negative gate voltages, relative to the source voltage, are applied to induce positive charges (holes) in the channel region of the device.
As an alternative to p-type organic semiconductor materials, N-type organic semiconductor materials can be used in TFTs as an alternative to p-type organic semiconductor materials, where the terminology “n-type” or “n-channel” indicates that positive gate voltages, relative to the source voltage, are applied to induce negative charges in the channel region of the device.
Moreover, one important type of TFT circuit, known as a complementary circuit, requires an n-type semiconductor material in addition to a p-type semiconductor material. See Dodabalapur et al. in “Complementary circuits with organic transistors” Appl. Phys. Lett. 1996, 69, 4227. In particular, the fabrication of complementary circuits requires at least one p-channel TFT and at least one n-channel TFT. Simple components such as inverters have been realized using complementary circuit architecture. Advantages of complementary circuits, relative to ordinary TFT circuits, include lower power dissipation, longer lifetime, and better tolerance of noise. In such complementary circuits, it is often desirable to have the mobility and the on/off ratio of an n-channel device similar in magnitude to the mobility and the on/off ratio of a p-channel device. Hybrid complementary circuits using an organic p-type semiconductor and an inorganic n-type semiconductor are known, as described in Dodabalapur et al. (Appl. Phys. Lett. 1996, 68, 2264.), but for ease of fabrication, an organic n-channel semiconductor material would be desired in such circuits.
Only a limited number of organic materials have been developed for use as a semiconductor n-channel in TFTs. One such material, buckminsterfullerene C60, exhibits a mobility of 0.08 cm2/Vs but is considered unstable in air. See R. C. Haddon, A. S. Perel, R. C. Morris, T. T. M. Palstra, A. F. Hebard and R. M. Fleming, “C60 Thin Film Transistors” Appl. Phys. Let. 1995, 67, 121. Perfluorinated copper phthalocyanine has a mobility of 0.03 cm2/Vs, and is generally stable to air operation, but substrates must be heated to temperatures above 100° C. in order to maximize the mobility in this material. See “New Air-Stable n-Channel Organic Thin Film Transistors” Z. Bao, A. J. Lovinger, and J. Brown J. Am. Chem, Soc. 1998, 120, 207. Other n-channel semiconductors, including some based on a naphthalene framework, have also been reported, but with lower mobilities. See Laquindanum et al., “n-Channel Organic Transistor Materials Based on Naphthalene Frameworks,” J. Am. Chem, Soc. 1996, 118, 11331. One such naphthalene-based n-channel semiconductor material, tetracyanonaphthoquino-dimethane (TCNNQD), is capable of operation in air, but the material has displayed a low on/off ratio and is also difficult to prepare and purify.
Aromatic tetracarboxylic diimides, based on a naphthalene aromatic framework, have also been demonstrated to provide, as an n-type semiconductor, n-channel mobilities up to 0.16 cm2/Vs using top-contact configured devices where the source and drain electrodes are on top of the semiconductor. Comparable results could be obtained with bottom contact devices, that is, where the source and drain electrodes are underneath the semiconductor, but a thiol underlayer needed to be applied between the electrodes, which had to be gold, and the semiconductor. See Katz et al. “Naphthalenetetracarboxylic Diimide-Based n-Channel Transistor Semiconductors: Structural Variation and Thiol-Enhanced Gold Contacts” J. Am. Chem. Soc. 2000 122, 7787; “A Soluble and Air-stable Organic Semiconductor with High Electron Mobility” Nature 2000 404, 478; Katz et al., European Patent Application EP1041653 or U.S. Pat. No. 6,387,727. In the absence of the thiol underlayer, the mobility of the compounds of Katz et al. was found to be orders of magnitude lower in bottom-contact devices. U.S. Pat. No. 6,387,727 B1 to Katz et al. discloses fused-ring tetracarboxylic diimide compounds, one example of which is N,N′-bis(4-trifluoromethyl benzyl)naphthalene-1,4,58,-tetracarboxylic acid diimide. Such compounds are pigments that are easier to reduce. The highest mobilities reported in U.S. Pat. No. 6,387,727 B1 to Katz et al. was between 0.1 and 0.2 cm2/Vs, for N,N′-dioctyl naphthalene-1,4,5,8-tetracarboxylic acid diimide.
Relatively high mobilities have been measured in films of naphthalene tetracarboxylic diimides having linear alkyl side chains using pulse-radiolysis time-resolved microwave conductivity measurements. See Struijk et al. “Liquid Crystalline Perylene Diimides: Architecture and Charge Carrier Mobilities” J. Am. Chem. Soc. Vol. 2000, 122, 11057.
US Patent Publication No. 2002/0164835 to Dimitrakopoulos et al. discloses improved n-channel semiconductor films made of perylene tetracarboxylic acid diimide compounds, as compared to naphthalene-based compounds, one example of which is N,N′-di(n-1H,1H-perfluorooctyl)perylene-3,4,9,10-tetracarboxylic acid diimide. Substituents attached to the imide nitrogens in the diimide structure comprise alkyl chains, electron deficient alkyl groups, electron deficient benzyl groups, the chains preferably having a length of four to eighteen atoms. Devices based on materials having a perylene framework used as the organic semiconductor have led to low mobilities, for example 10−5 cm2/Vs for perylene tetracarboxylic dianhydride (PTCDA) and 1.5×10−5 cm2/Vs for NN′-diphenyl perylene tetracarboxylic acid diimide (PTCDI-Ph). See Horowitz et al. in “Evidence for n-Type Conduction in a Perylene Tetracarboxylic Diimide Derivative” Adv. Mater. 1996, 8, 242 and Ostrick, et al. J. Appl. Phys. 1997, 81, 6804.
US Patent Publication No. 2005/0176970 to Marks et al. discloses improved n-channel semiconductor films made of mono and diimide perylene and naphthalene compounds, N- and core substituted with electron withdrawing groups. Substituents attached to the imide nitrogens in the diimide structure can be selected from alkyl, cycloalkyl, substituted cycloalkyl, aryl and substituted aryl moieties. However, Marks et al. do not see any advantage of using cycloalkyl groups on the imide nitrogens. Accordingly, mobilities obtained from perylene diimides containing of N-octyl and N-cyclohexyl are virtually indistinguishable (page 10, Column 1, Example 10). Furthermore, the highest mobilities reported in US Patent Pub. No. 2005/0176970 A1 to Marks et al. were 0.2 cm2/Vs. Marks et al. show no experimental data with respect to naphthalene compounds, but require that their core be dicyano disubstituted.
U.S. Ser. No. 11/567,954 filed Dec. 7, 2006 to Shukla et al. discloses that configurationally controlled N,N′-disubstituted-1,4,5,8-naphthalenetetracarboxylic acid diimides exhibit superior n-type semiconducting properties in a thin film transistor device compared to configurationally mixed 1,4,5,8-naphthalenetetracarboxylic acid diimides, in the case of such compounds bearing a 4-substituted cyclohexyl group on one or both imide nitrogens.
As discussed above, a variety of 1,4,5,8-naphthalenetetracarboxylic acid diimides have been made and tested for n-type semiconducting properties. In general, these materials, as an n-type semiconductor, have provided n-channel mobilities up to 0.16 cm2/Vs using top-contact configured devices. There is a need in the art for new and improved organic semiconductor materials for transistor materials and improved technology for their manufacture and use. There is especially a need for n-type semiconductor materials exhibiting significant mobilities and current on/off ratios in organic thin film transistor devices.
In particular, to 1,4,5,8-naphthalenetetracarboxylic acid diimides exhibiting superior n-type semiconducting properties compared to 1,4,5,8-naphthalenetetracarboxylic acid diimides bearing alkyl groups are desired.